The Mode of Action of Recombinant Mycobacterium tuberculosis Shikimate Kinase: Kinetics and Thermodynamics Analyses

Tuberculosis remains as one of the main cause of mortality worldwide due to a single infectious agent, Mycobacterium tuberculosis. The aroK-encoded M. tuberculosis Shikimate Kinase (MtSK), shown to be essential for survival of bacilli, catalyzes the phosphoryl transfer from ATP to the carbon-3 hydroxyl group of shikimate (SKH), yielding shikimate-3-phosphate and ADP. Here we present purification to homogeneity, and oligomeric state determination of recombinant MtSK. Biochemical and biophysical data suggest that the chemical reaction catalyzed by monomeric MtSK follows a rapid-equilibrium random order of substrate binding, and ordered product release. Isothermal titration calorimetry (ITC) for binding of ligands to MtSK provided thermodynamic signatures of non-covalent interactions to each process. A comparison of steady-state kinetics parameters and equilibrium dissociation constant value determined by ITC showed that ATP binding does not increase the affinity of MtSK for SKH. We suggest that MtSK would more appropriately be described as an aroL-encoded type II shikimate kinase. Our manuscript also gives thermodynamic description of SKH binding to MtSK and data for the number of protons exchanged during this bimolecular interaction. The negative value for the change in constant pressure heat capacity (ΔCp) and molecular homology model building suggest a pronounced contribution of desolvation of non-polar groups upon binary complex formation. Thermodynamic parameters were deconvoluted into hydrophobic and vibrational contributions upon MtSK:SKH binary complex formation. Data for the number of protons exchanged during this bimolecular interaction are interpreted in light of a structural model to try to propose the likely amino acid side chains that are the proton donors to bulk solvent following MtSK:SKH complex formation. © 2013 Rosado et al.

The heat capacity of superfluid ^4He in the presence of a constant heat flux near Tλ

We present the first experimental evidence that the heat capacity of superfluid ⁴He, at temperatures very close to the lambda transition temperature, T_λ,is enhanced by a constant heat flux, Q. The heat capacity at constant Q, C_Q,is predicted to diverge at a temperature T_c(Q) < T_λ at which superflow becomes unstable. In agreement with previous measurements, we find that dissipation enters our cell at a temperature, T_DAS(Q),below the theoretical value, T_c(Q). Our measurements of C_Q were taken using the discrete pulse method at fourteen different heat flux values in the range 1µW/cm² ≤ Q≤ 4µW /cm². The excess heat capacity ∆C_Q we measure has the predicted scaling behavior as a function of T and Q:∆C_Q • t^α ∝ (Q/Q_c)², where Q_cT) ~ t^2ν is the critical heat current that results from the inversion of the equation for T_c(Q). We find that if the theoretical value of T_c( Q) is correct, then ∆C_Q is considerably larger than anticipated. On the other hand,if T_c(Q)≈ T_DAS(Q),then ∆C_Q is the same magnitude as the theoretically predicted enhancement.

Chemical Reactors. Problem 2: Constant pressure adiabatic stirred batch reactor with variable heat capacities (2011-2012 Course)

Wording of problem 2 (week 3, 17/10/11).

Chemical Reactors. Problem 2: Constant pressure adiabatic stirred batch reactor with variable heat capacities. Solution (2011-2012 Course)

Chemical Reaction Engineering. Course 2011-12. Solution of problem 2: constant pressure adiabatic stirred batch reactor with variable heat capacities.

Heat-Capacity Measurements - Progress In Experimental-Techniques

The heat capacity of a substance is related to the structure and constitution of the material and its measurement is a standard technique of physical investigation. In this review, the classical methods are first analyzed briefly and their recent extensions are summarized. The merits and demerits of these methods are pointed out. The newer techniques such as the a.c. method, the relaxation method, the pulse methods, the laser flash calorimetry and other methods developed to extend the heat capacity measurements to newer classes of materials and to extreme conditions of sample geometry, pressure and temperature are comprehensively reviewed. Examples of recent work and details of the experimental systems are provided for each method. The introduction of automation in control systems for the monitoring of the experiments and for data processing is also discussed. Two hundred and eight references and 18 figures are used to illustrate the various techniques.

Low-temperature heat capacity and standard molar enthalpy of formation of 9-fluorenemethanol (C14H12O)

Low-temperature heat capacities of the 9-fluorenemethanol (C14H12O) have been precisely measured with a small sample automatic adiabatic calorimeter over the temperature range between T = 78 K and T = 390 K. The solid-liquid phase transition of the compound has been observed to be T-fus = (376.567 +/- 0.012) K from the heat-capacity measurements. The molar enthalpy and entropy of the melting of the substance were determined to be Delta(fus)H(m) = (26.273 +/- 0.013) kJ (.) mol(-1) and Delta(fus)S(m) = (69.770 +/- 0.035) J (.) K-1 (.) mol(-1). The experimental values of molar heat capacities in solid and liquid regions have been fitted to two polynomial equations by the least squares method. The constant-volume energy and standard molar enthalpy of combustion of the compound have been determined, Delta(c)U(C14H12O, s) = -(7125.56 +/- 4.62) kJ (.) mol(-1) and Delta(c)H(m)degrees(C14H12O, s) = -(7131.76 +/- 4.62) kJ (.) mol(-1), by means of a homemade precision oxygen-bomb combustion calorimeter at T = (298.15 +/- 0.001) K. The standard molar enthalpy of formation of the compound has been derived, Delta(f)H(m)degrees (C14H12O, s) = -(92.36 +/- 0.97) kJ (.) mol(-1), from the standard molar enthalpy of combustion of the compound in combination with other auxiliary thermodynamic quantities through a Hess thermochemical cycle. (C) 2004 Elsevier Ltd. All rights reserved.

Characterization of commercial double-walled carbon nanotube material : composition, structure, and heat capacity

A purified commercial double-walled carbon nanotube (DWCNT) sample was investigated by transmission electron microscopy (TEM), thermogravimetry (TG), and Raman spectroscopy. Moreover, the heat capacity of the DWCNT sample was determined by temperature-modulated differential scanning calorimetry in the range of temperature between -50 and 290 °C. The main thermo-oxidation characterized by TG occurred at 474 °C with the loss of 90 wt% of the sample. Thermo-oxidation of the sample was also investigated by high-resolution TG, which indicated that a fraction rich in carbon nanotube represents more than 80 wt% of the material. Other carbonaceous fractions rich in amorphous coating and graphitic particles were identified by the deconvolution procedure applied to the derivative of TG curve. Complementary structural data were provided by TEM and Raman studies. The information obtained allows the optimization of composites based on this nanomaterial with reliable characteristics.

The heat capacity of liquid carbon disulfide + acetonitrile, especially near the upper critical solution temperature

The heat capacity Cp of the binary liquid system CS2 + CH3CN has been studied. This system has an upper critical solution temperature To ≈ 323.4 K and a critical mole fraction of CS2xo ≈ 0.5920. Measurements were made both for mixtures close to and far away from the critical region. The heat capacity of the mixture with x = xo exhibits a symmetric logarithmic anomaly around Tc, which is apparently preserved even for compositions in the immediate vicinity of xc. For compositions far away from xc, only a normal rise in Cp over the covered temperature range is observed.

High-temperature heat capacity and heat content of CaCu3Ti4O12 (CCTO)

The isobaric heat capacity of CaCu3Ti4O12 (CCTO) was measured from 300 to 1100 K using differential scanning calorimetry (DSC). The results were verified using drop calorimetric measurement of enthalpy increment (H-T - H-298.15) at T= 973 and 1073 K. The samples were dropped from room temperature into a calorimeter maintained at high temperature. The results show small negative deviation from Neumann-Kopp rule. The enthalpy and entropy increments are computed as a function of temperature and compared with values available in the literature. The results obtained in this study are consistent with available information on enthalpy and Gibbs energy of formation of CCTO.

Studies in bubble formation—II bubble formation under constant pressure conditions

Bubble formation under constant pressure conditions has been investigated for wide range of variation of liquid properties.Air bubbles were formed from single horizontal orifices submerged in liquids whose viscosity varied from 1·0 to 600 cPs and surface tension from 37 to 72 dyn/cm. Air flow rate was varied from 2 to 250 cm3/sec and the orifice diameter from 0·0515 to 0·4050 cm.

Heat capacity measurements on Ge20Se80−xBix glasses

The specific heat Cp of glassy Ge20Se80−xBix (0 ≤ × ≤ 12) samples is investigated. The Cp at 323K and the ΔCp at glass transition temperature Tg1 show anomalous features around x = 8 at.%, where p−n conduction type inversion also take place. These features are discussed in the light of Phillips model of phase separation in these glasses at the microscopic level.

3-Dimensional laminar boundary-layer in a constant-pressure diverging

larity solution is obtained for laminar 3D constant pressure flow with lateral streamline divergence. The similarity solution is shown to reduce to a Blasius solution for 2D flow over a flat plate. Measurements of velocity profiles are made to compare the similarity solution and are found to be in excellent agreement with the prediction

Constant pressure laminar, transitional and turbulent flows - An approximate unified treatment

A nondimensional number that is constant in two-dimensional, incompressible and constant pressure laminar and fully turbulent boundary, layer flows has been proposed. An extension of this to constant pressure transitional flow is discussed.